Sulphone-morpholine compounds of the amino-anthraquinone series



Patented Oct. 30, 1934 UNITED STATES PATENT OFFICE 1,978,777 3 SULPHONE -MORPHOLIN E COMPOUNDS THE AMINO -ANTHRAQUINONE SERIES Karl Zahn, Frankfort-on-the-Main-Hochst, and i Willi Giidke, Hofheim-on-the-Taunus, Germany, assignors to General Aniline Works, Inc., New York, N. 15., a corporation of Delaware N 0 Drawing.

Application -December 15, 1933,

Serial No. 702,644. In Germany December 17,

1932 A 5 Claims.

Our-present invention relates to new sulfurand-nitrogen-containing derivatives of the anthraquinone series; more particularly it relates to new compounds of the general formula:

0 GlElz,

where X stands for hydrogen or methyl and R represents a radical of, the benzene, naphthalene or diphenyl series. I

Our new products are obtainable by causing a compound of the general formula:

wherein'X stands=for hydrogen or methyl and Y for -a chlorine or bromine atom, toreact' with a primary amine of the benzene; naphthalene-or diphenyl series. The reaction is carried out in a suitable solvent or diluent, preferably in the presence of an acid binding agent, such as an alkali metal acetate, and, lfTdESlIGd, in the presence of a small quantity ofa catalytically acting substance such as copper or 'a'copper compound.

The above defined starting materials are obtainable by treating thio norpholine compounds of the anthraquinone series having the general formula:

f) .UHN OH:

tion, but they are not intended to limit it thereto; the parts are by weight unless otherwise stated: 4

(1) parts of the anthraquinone derivative of the following probable constitution:

are kept gently boiling with 800 parts of aniline and 23 parts of anhydrous sodiumacetate, for 8 hours, while stirring. The somewhat cooled melt 9m is then introduced into alcohol, while stirring, and

the reaction product? is isolated in the usual manher. It forms, when recrystallized from chlorobenzene, greenish dark blue laminae melting at 256 0. to 257 0. and has the" following constitution:

The anthraquinone derivative used as starting material melts at 256 C. to 258 C. It is obtainable by oxidizing the anthraquinone-l.2-dihydropara-thioazine melting at 171 C. to 172 C. de-

5 scribed in Example 1 of U. S. patent specification No. 1,709,986, by means of hydrogen peroxide in a solution of glacial acetic acid and then brominating in nitrobenzene the oxidation product which constitutes brown brilliant laminae melting at 291 C. to 292 C.

The dyestuff base made according to the first paragraph of this example may also be obtained by using as starting material, instead of the bromine derivative, the corresponding chlorine derivative.

20 parts of the dyestuff base are introduced, while stirring, into a mixture of 160 partsof sulphuric acid monohydrate and 100 parts of fuming sulphuric acid containing 20 per cent. of sulphuric anhydride, and stirring is continued until a sample taken is completely soluble in water. By pouring the mixture intowater and adding sodiumchloride, a dyestuff is precipitated in the form of a dark-blue powder which dyes wool from an acid bath clear blue tints of good fastness properties. The dyestuff corresponds to the following formula:

0 HN OH;

(3) By causing the starting material described in Example 1 to react in a similar manner with 4- aminodiphenyl, a dyestuff base is obtained in the hours to 200 C. The product is worked up in (2) By using insteadjof the aniline indicated o HN/ 0112 By sulphonating it a dyestuff is obtained which dyes wool fast green tints.

(4) The starting material used in Example 1 is heated with para-cyclohexylaniline for about 2 known manner. A dyestuff base is obtained in the form of dark blue crystals melting at 232 C. to 233 C. It corresponds to the following formula:

0 EN CH2 The sulphonic acid obtainable therefrom dyes x When redissolved from benzene, it forms dark green crystals melting at 222C. to 223 C. By sulphonating it a dyestuff is obtained which dyes wool greenish blue tints.

(6) 50 part's of the anthraquinone derivative phenyl for a short timeto about 250 C. and-'the of the following probable constitution: product is worked up as usual. A color base is obtained which crystallizes in the form of dark violet needles melting at a temperature above 300 C. The sulphonic acidtmade therefrom dyes 80 wool greenish blue tints, The sulphonated compound has the following constitution:

om /$H 0 EN CH, H i H melting at a temperature above 300 (3., are causedto react inthe usual manner with para- 90 toluidin'e and'anhydrous sodiumacetate. A dyestufit is obtained which crystallizes from chloroa benzene in the form of reddish dark-blue needles, QQ Q meltingat2811 C. to 288 C. The sulphonic acid v made therefrom dyes wool blue tints. The dye- W a 2O stufl'has the'following constitution: The compoundsnf the general for 1 O JO, Jo,

NH N H wherein X stands for hydrogen or methyl and R represents a radical of the benzene, naphno thalene or diphenyl series. 6 2. The compounds of the general formula:

The anthraquinone derivative used as starting X Y 3 material is obtainable by causing monochloro- I it acetone to react with the sodium salt of l-amino- 115 2-mercapto-anthraquinone and boiling the thus HN CH2 formed condensation product in chlorobenzene A while adding glacial acetic acid whereby ring closure takes place according to the following probable equation: 1m

CH3 OH NH 0= B J iLsom I NH: HN CH wherein X stands for hydrogen or methyl and 1% l R represents a radical of the benzene, naphthalene or diphenyl series which compounds are soluble in water and dye the animal fiber from v an acid bath. Y 3. The compound of the formula: 190

The product obtained is hydrogenated and the resulting compound melting at 229 C. to 230 C., o EN 011,

- of the formula: OH: 0 so:

6B O HN/ \OH: 5'

is oxidized by means of hydrogen peroxide in a solution of glacial acetic acid and then brominated being soluble in water and dyeing wool from an in nitrobenzene. acid bath greenish blue tints, the corresponding g (7) The starting material used in Example 6 unsulphonated compound having a melting point is heated in a suitable manner with 4-aminodiof 227 C. to 228 C.

CHI

SOQH

being soluble inwater and dyeing wool from an acid bath blue tints, the corresponding unsulphonated compound having a melting point of 287 C. to 288 C.

5. The compound of the formula:

$1: E uN CH2,

--S0g r being soluble in water and dyeing woolfrom an acidbath greenish blue tints, the unsulphonated compound having a melting point of above 300 C.

KARL ZAHN. WILLI GADKE. 

